DE102016122626A1 - Polymerizable sulfobetaines - Google Patents

Polymerizable sulfobetaines Download PDF

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DE102016122626A1
DE102016122626A1 DE102016122626.2A DE102016122626A DE102016122626A1 DE 102016122626 A1 DE102016122626 A1 DE 102016122626A1 DE 102016122626 A DE102016122626 A DE 102016122626A DE 102016122626 A1 DE102016122626 A1 DE 102016122626A1
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alkyl
phenyl
group
nhr
ionic compounds
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Annett Halbhuber
Bernd Strehmel
Walther Sebastian
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Hochschule Niederrhein
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    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/60—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with hydrocarbon radicals, substituted by oxygen or sulfur atoms, attached to ring nitrogen atoms
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    • C07C311/03—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atoms of the sulfonamide groups bound to hydrogen atoms or to acyclic carbon atoms
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    • C07C311/02—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
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    • C07C311/15—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C311/20—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the sulfonamide groups bound to a carbon atom of a ring other than a six-membered aromatic ring
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    • C07C311/30—Sulfonamides, the carbon skeleton of the acid part being further substituted by singly-bound nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/31—Sulfonamides, the carbon skeleton of the acid part being further substituted by singly-bound nitrogen atoms, not being part of nitro or nitroso groups having the sulfur atoms of the sulfonamide groups bound to acyclic carbon atoms
    • C07C311/32—Sulfonamides, the carbon skeleton of the acid part being further substituted by singly-bound nitrogen atoms, not being part of nitro or nitroso groups having the sulfur atoms of the sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
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    • C07C311/48—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom
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    • C07C381/04—Thiosulfonates
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    • C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D207/06—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with radicals, containing only hydrogen and carbon atoms, attached to ring carbon atoms
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    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
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    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
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    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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Abstract

Die Erfindung betrifft Sulfobetainverbindungen, ein Verfahren zu deren Herstellung und die Verwendungen von Sulfobetainverbindungen zur Herstellung von anti-mikrobiellen Materialien, anti-statischen Materialien, anti-fouling Materialien, Druckfarben, oberflächenaktiven Materialien, Beschichtungen und Lithografische Materialien, zur Herstellung von Herbiziden, Fungiziden und Polymeren sowie zur Anwendung in der 2D-Gelelektrophorese und zur Anti-Haft-Beschichtung von Oberflächen.The invention relates to sulfobetaine compounds, a process for their preparation and the uses of sulfobetaine compounds for the production of anti-microbial materials, anti-static materials, anti-fouling materials, printing inks, surface-active materials, coatings and lithographic materials, for the production of herbicides, fungicides and Polymers and for use in 2D gel electrophoresis and for non-stick coating of surfaces.

Description

Die Erfindung betrifft Sulfobetainverbindungen, ein Verfahren zu deren Herstellung und die Verwendungen von Sulfobetainverbindungen als Fungizide, Herbizide und Polymere.The invention relates to sulfobetaine compounds, a process for their preparation and the uses of sulfobetaine compounds as fungicides, herbicides and polymers.

Als Betaine wird eine Stoffklasse organisch-chemischer Verbindungen bezeichnet, die in ihrer Molekülstruktur sowohl eine positive als auch eine negative Ladung tragen, nach außen hin aber ungeladen sind. Sulfobetaine sind wie die Betaine zwitterionische-Verbindungen, die jedoch anstatt der Carboxylatgruppe (-COO-) meist einen als Sulfoalkylgruppe vorliegenden, SO3- Rest enthalten. In Betainen und Sulfobetainen können sich diese Ladungen, anders als bei Zwitterionen, nicht durch Protonenwanderung ausgleichen.Betaine is a class of organic chemical compounds that carry both a positive and a negative charge in their molecular structure but are uncharged towards the outside. Sulfobetaines, like the betaines, are zwitterionic compounds, but instead of the carboxylate group (-COO - ), they generally contain an SO 3 radical present as a sulfoalkyl group. In betaines and sulfobetaines, unlike zwitterions, these charges can not be balanced by proton migration.

Sulfobetaine spielen in der Industrie eine Rolle als Amphotenside in Shampoos und Schaumbädern. In der Biochemie werden Sulfobetaine zur Lösung von Proteinen eingesetzt, z. B. bei der 2D-Gelelektrophorese und zur Anti-Haft-Beschichtung von Oberflächen, wie z. B. bei Quantenpunkten. So ist bekannt, dass zweizähnige, zwitterionische Dihydroliponsäure-Sulfobetain (DHLA-SB) Liganden eine günstige Alternative zu Polyethylenglykol-beschichteten Nanopartikel sind, da sie kleine Größen eine geringe unspezifische Adsorption aufweisen, optische Eigenschaften konservieren und eine ausgezeichnete Stabilität über die Zeit unabhängig von pH-Wert und Salzgehalt aufweisen. Solche Verbindungen können leicht als Quantenpunkte funktionalisiert werden.Sulfobetaines play a role in the industry as amphoteric surfactants in shampoos and bubble baths. In biochemistry, sulfobetaines are used to dissolve proteins, e.g. B. in the 2D gel electrophoresis and anti-adhesion coating of surfaces such. At quantum dots. Thus, bidentate, zwitterionic dihydrolipoic acid sulfobetaine (DHLA-SB) ligands are known to be a favorable alternative to polyethylene glycol-coated nanoparticles, since they have small non-specific adsorption small sizes, conserve optical properties, and have excellent stability over time regardless of pH Value and salinity. Such compounds can easily be functionalized as quantum dots.

Ferner ist in der US 24 33 997 A eine neue Klasse von organischen quartären Ammoniumverbindungen, insbesondere von quartären Ammoniumsulfonhaliden und Verfahren zu deren Herstellung über Ammoniumsulfonhalogenide beschrieben, wobei die Verbindungen als oberflächenaktives Tensid oder als Hilfsstoffe bei der Herstellung von Fungiziden, Insektiziden, Imprägnierungsmittel verwendet werden und als Intermediat bei der Herstellung von Farbstoffen, Pharmazeutika und verwandten Produkte auftreten können.Furthermore, in the US 24 33 997 A describe a new class of organic quaternary ammonium compounds, in particular quaternary ammonium sulfonyl halides, and processes for their preparation via ammonium sulfone halides, the compounds being used as surface-active surfactants or as adjuvants in the preparation of fungicides, insecticides, impregnants and as intermediates in the preparation of dyes, Pharmaceuticals and related products can occur.

Verbindungen der oben genannten Art können durch verschiedene Verfahren hergestellt werden. Zum Beispiel kann eine organische Sulfonsäure, die ein mit Wasserstoff-substituiertes Stickstoffatom enthält, mit Halogenierungsmitteln wie Phosphorpentachlorid, Chlor, Sulfonsäure und dergleichen umgesetzt werden. Das Reaktionsprodukt wird dabei durch Kondensation, üblicherweise unter Normaldruck erhalten, wobei das Halogenierungsmittel und die Nebenprodukte durch Absenken des Drucks aus dem Reaktionsgefäß entfernt werden.Compounds of the above type can be prepared by various methods. For example, an organic sulfonic acid containing a hydrogen-substituted nitrogen atom may be reacted with halogenating agents such as phosphorus pentachloride, chlorine, sulfonic acid and the like. The reaction product is obtained by condensation, usually under atmospheric pressure, wherein the halogenating agent and the by-products are removed by lowering the pressure from the reaction vessel.

Problematisch am bisher bekannten Stand der Technik ist daher, dass die beabsichtigte Herstellung von Sulfobetainhalogeniden, insbesondere polymerisierbarer Sulfobetainhalogenide über Destillation erfolgt, die eine nachfolgende Abtrennung der Edukte und Produkte zeitaufwendig und teuer macht.A problem in the prior art, therefore, is that the intended production of Sulfobetainhalogeniden, in particular polymerizable sulfobetaine halides via distillation, which makes subsequent separation of the reactants and products time-consuming and expensive.

Die Erfindung hat vorliegend die Aufgabe, quartäre Ammoniumverbindungen zu synthetisieren, die über leicht zugängliche Zwischenprodukte in Form von Ammoniumsulfonhalogenide erhalten werden und polymerisierbar sein können und die Nachteile des bekannten Stands der Technik überwinden.The object of the present invention is to synthesize quaternary ammonium compounds which can be obtained via readily available intermediates in the form of ammonium sulfone halides and which can be polymerizable and overcome the disadvantages of the known prior art.

Die Aufgabe wird erfindungsgemäß durch die Kennzeichen der unabhängigen Ansprüche 1, 7 und 13 gelöst.The object is achieved by the characteristics of the independent claims 1, 7 and 13.

Erfindungsgemäß werden zur Lösung der Aufgabe ionische Verbindungen beansprucht, die pro Molekül mindestens eine Ammoniumgruppe, mindestens eine Sulfonylgruppe, mindestens eine Cn-Alkyl-Gruppe, Cn-Alkyl-Gruppe-R4, Cn-Alkyl-OR4-Gruppe, Cn-Alkyl-SR4-Gruppe oder Cn-Alkyl-NHR4-Gruppe enthält, wobei R4 = Cn-Alkyl, CO-CH3, -CO-CH2-CH3, -CO-NH2, Phenyl, (CH2)n-Phenyl, -(CH2)n-Phenyl-CH-CH3, (CH2)n-N(CH3)2-(CH2)n-CH3, -CO-Phenyl-(CH2)n-CH3, -CO-NH-(CH-(CH3)2) und an die Cn-Alkyl tragende Ammoniumgruppe mindestens eine Gruppe Z gebunden ist, wobei Z = Cn-Alkyl-SO2-Y, -(CH2)n-SO2-Y, -(CH2)n-O-SO2-Y, -Phenyl-S-SO2-Y umfasst und Y = O, Cl, -OR4, -SR4, -NH-Phenyl, -NR4, -NH-Phenyl-SO2-NH2, - NH-R4, -N-SO2-(CmF2m+1), -N-CN, -C(CN)2, umfasst, und n = 0 bis 18 und m = 1 bis 10 ist, sowie deren Salze, Solvate und Solvate dieser Salze.According to the invention, ionic compounds which per molecule have at least one ammonium group, at least one sulfonyl group, at least one C n -alkyl group, C n -alkyl group-R 4 , C n -alkyl-OR 4 -group, are claimed for achieving the object. C n -alkyl-SR 4 group or C n -alkyl-NHR 4 group, where R 4 = C n -alkyl, CO-CH 3 , -CO-CH 2 -CH 3 , -CO-NH 2 , phenyl, (CH 2) n -phenyl, - (CH 2) n -phenyl-CH-CH 3, (CH 2) n -N (CH 3) 2 - (CH 2) n -CH 3, -CO-phenyl (CH 2 ) n -CH 3 , -CO-NH- (CH- (CH 3 ) 2 ) and to the C n -alkyl-bearing ammonium group at least one group Z is bound, where Z = C n -alkyl-SO 2 -Y, - (CH 2 ) n -SO 2 -Y, - (CH 2 ) n -O-SO 2 -Y, -phenyl-S-SO 2 -Y and Y = O, Cl, -OR 4 , -SR 4 , -NH-phenyl, -NR 4 , -NH-phenyl-SO 2 -NH 2 , - NH-R 4 , -N-SO 2 - (C m F 2m + 1 ), -N-CN, -C (CN) 2 , and n = 0 to 18 and m = 1 to 10, and their salts, solvates and solvates of these salts.

Ferner werden erfindungsgemäß ionische Verbindungen beansprucht, die pro Molekül mindestens eine Ammoniumgruppe, mindestens eine Sulfonylgruppe, mindestens eine Cn-Alkyl-R4-Gruppe, eine Cn-Alkyl-OR4-Gruppe, Cn-Alkyl-SR4-Gruppe oder Cn-Alkyl-NHR4-Gruppe enthält, wobei R4= Acryl, -Methacryl, -Vinyl, Cn-Alkyl, CO-CH3, -CO-CH2-CH3, -CO-(CH2)n-CH=CH-Phenyl, Phenyl, (CH2)n-Phenyl, - (CH2)n-Phenyl-CH-CH3, (CH2)n-N(CH3)2-(CH2)n-CH3, -CO-Phenyl-(CH2)n-CH3, - (CH2)n-C≡CH, -CO-NH-(CH-(CH3)2) und an die Cn-Alkyl tragende Ammoniumgruppe mindestens eine Gruppe Z gebunden ist,
wobei
Z = Cn-Alkyl-SO2-Y, -(CH2)n-SO2-Y, -(CH2)n-O-SO2-Y, -Phenyl-S-SO2-Y, -CH-(CH3)2-SO2-Y umfasst und Y= O, Cl, -OR4, -SR4, -NH-Phenyl, -NR4, -NH-Phenyl-SO2-NH2, -NH-R4, -N-SO2-(CmF2m+1), -N-CN, -C(CN)2 umfasst, und n = 0 bis 18 und m = 1 - 10 ist, sowie deren Salze, Solvate und Solvate dieser Salze.Furthermore, according to the invention, ionic compounds are claimed which contain per molecule at least one ammonium group, at least one sulfonyl group, at least one C n -alkyl-R 4 group, one C n -alkyl-OR 4 group, C n -alkyl-SR 4 group or C n -alkyl-NHR 4 group, where R 4 = acryl, methacryl, vinyl, C n -alkyl, CO-CH 3 , -CO-CH 2 -CH 3 , -CO- (CH 2 ) n -CH = CH-phenyl, phenyl, (CH 2 ) n -phenyl, - (CH 2 ) n -phenyl-CH-CH 3 , (CH 2 ) n N (CH 3 ) 2 - (CH 2 ) n -CH 3, -CO-phenyl - (CH 2 ) n -CH 3, - (CH 2 ) n -C≡CH, -CO-NH- (CH (CH 3 ) 2 ) and to the C n -alkyl-bearing ammonium group at least one group Z is bound,
in which
Z = C n -alkyl-SO 2 -Y, - (CH 2 ) n -SO 2 -Y, - (CH 2 ) n -O-SO 2 -Y, -phenyl-S-SO 2 -Y, -CH - (CH 3 ) 2 -SO 2 -Y and Y = O, Cl, -OR 4 , -SR 4 , -NH-phenyl, -NR 4 , -NH-phenyl-SO 2 -NH 2 , -NH- R 4 , -N-SO 2 - (C m F 2m + 1 ), -N-CN, -C (CN) 2 , and n = 0 to 18 and m = 1-10, and their salts, solvates and solvates of these salts.

Weiterhin werden ionische Verbindungen der allgemeinen Formel (1) beansprucht,

Figure DE102016122626A1_0001
sowie deren Salze, Solvate und Solvate dieser Salze,
wobei

Z =
Cn-Alkyl-SO2-Y, -(CH2)n-SO2-Y, -(CH2)n-O-SO2-Y, -Phenyl-S-SO2-Y, -CH-(CH3)2-SO2- Y,
R1 =
H, Cn-Alkyl, Cn-Alkyl-R4, Cn-Alkyl-OR4, Cn-Alkyl-SR4 oder Cn-Alkyl-NHR4
R2 =
H, Cn-Alkyl, Cn-Alkyl-R4, Cn-Alkyl-OR4, Cn-Alkyl-SR4 oder Cn-Alkyl-NHR4
R3 =
H, Cn-Alkyl, Cn-Alkyl-R4, Cn-Alkyl-OR4, Cn-Alkyl-SR4 oder Cn-Alkyl-NHR4
R1 =
R2 = R3 = mehrfach, allein oder unabhängig voneinander sein kann, sowie (C1nH2n-O)n, (C1nH2n)n, 1,4-Diazobicylco [2.2.] octane, 1-Azoniabicyclo [2.2.2] octane, 4-Aza-1-azoniabicyclo [2.2.2] octane umfasst,
A =
N, Imidazole, Pyridine, Pyrimidine, Triazole, Tetrazole, Benzimidazole, Thiazole, Thiadiazole, Benzothiazole, Morpholine
R4 =
Acryl, -Methacryl, -Vinyl, Cn-Alkyl, CO-CH3, -CO-CH2-CH3, -CO-(CH2)n-CH=CH-Phenyl, Phenyl, (CH2)n-Phenyl, -(CH2)n-Phenyl-CH-CH3, (CH2)n-N(CH3)2-(CH2)n-CH3, -CO-Phenyl-(CH2)n-CH3, -(CH2)n-C=CH, -CO-NH-(CH-(CH3),
Y =
O, Cl, -OR4, -SR4, -NH-Phenyl, -NR4, -NH-Phenyl-SO2-NH2, -NH-R4, -N-SO2-(CmF2m+1), -N-CN, -C(CN)2
X' =
Verbindung, die zumindest eine Hydrophobizität mit einem Verteilungskoeffizienten log Kow > 0 aufweist und
n =
0 - 18 umfasst und m = 1 - 10.
Furthermore, ionic compounds of the general formula (1) are claimed,
Figure DE102016122626A1_0001
 and their salts, solvates and solvates of these salts,
in which
Z =
C n -alkyl-SO 2 -Y, - (CH 2 ) n -SO 2 -Y, - (CH 2 ) n -O-SO 2 -Y, -phenyl-S-SO 2 -Y, -CH- ( CH 3 ) 2 -SO 2 - Y,
R 1 =
H, C n -alkyl, C n -alkyl-R 4 , C n -alkyl-OR 4 , C n -alkyl-SR 4 or C n -alkyl-NHR 4
R2 =
H, C n -alkyl, C n -alkyl-R 4 , C n -alkyl-OR 4 , C n -alkyl-SR 4 or C n -alkyl-NHR 4
R3 =
H, C n -alkyl, C n -alkyl-R 4 , C n -alkyl-OR 4 , C n -alkyl-SR 4 or C n -alkyl-NHR 4
R 1 =
R 2 = R 3 = may be multiple, alone or independently, and (C 1n H 2n -O) n , (C 1n H 2n ) n , 1,4-diazobicylco [2.2.] Octane, 1-azoniabicyclo [2.2 .2] octane, 4-aza-1-azoniabicyclo [2.2.2] octane,
A =
N, imidazoles, pyridines, pyrimidines, triazoles, tetrazoles, benzimidazoles, thiazoles, thiadiazoles, benzothiazoles, morpholines
R 4 =
Acrylic, methacrylic, vinyl, C n -alkyl, CO-CH 3 , -CO-CH 2 -CH 3 , -CO- (CH 2 ) n -CH = CH - phenyl, phenyl, (CH 2 ) n - Phenyl, - (CH 2 ) n -phenyl-CH-CH 3 , (CH 2 ) n -N (CH 3 ) 2 - (CH 2 ) n -CH 3 , -CO-phenyl- (CH 2 ) n -CH 3 , - (CH 2 ) n -C = CH, -CO-NH- (CH- (CH 3 ),
Y =
O, Cl, -OR 4 , -SR 4 , -NH-phenyl, -NR 4 , -NH-phenyl-SO 2 -NH 2 , -NH-R 4 , -N-SO 2 - (C m F 2m + 1 ), -N-CN, -C (CN) 2
X '=
Compound having at least one hydrophobicity with a distribution coefficient log Kow> 0 and
n =
0 - 18 and m = 1 - 10.

Es werden erfindungsgemäß Anionen eingesetzt, die einen Verteilungskoeffizienten log Kow › 0, d.h. eine Hydrophobizität aufweisen, die einen Phasenübergang des Reaktionsprodukts und damit eine Ausfällung des Reaktionsprodukts aus der wässrigen Phase ermöglicht. Kow ist dabei ein dimensionsloser Verteilungskoeffizient, der das Verhältnis der Konzentrationen einer Chemikalie in einem Zweiphasensystem aus einem organischen Lösungsmittel im speziellen Fall n-Octanol und Wasser angibt.Anions are used according to the invention which have a distribution coefficient log K ow > 0, ie a hydrophobicity which allows a phase transition of the reaction product and thus a precipitation of the reaction product from the aqueous phase. Kow is a dimensionless distribution coefficient, which indicates the ratio of the concentrations of a chemical in a two-phase system from an organic solvent in the special case n-octanol and water.

Der Kow-Wert ist insofern ein Modellmaß für das Verhältnis zwischen Lipophilie (Fettlöslichkeit) und Hydrophilie (Wasserlöslichkeit) einer Substanz. Die Erwartung ist, mit Hilfe des Octanol-Wasser-Verteilungskoeffizienten auch die Verteilungskoeffizienten dieses Stoffes in anderen Systemen mit einer wässrigen und einer lipophilen Phase abschätzen zu können. Kow ist größer als eins, wenn eine Substanz besser in fettähnlichen Lösungsmitteln wie n-Octanol löslich ist, kleiner als eins wenn sie besser in Wasser löslich ist. Entsprechend ist Log Kow positiv für lipophile und negativ für hydrophile Substanzen.The Kow value is thus a model measure of the relationship between lipophilicity (lipid solubility) and hydrophilicity (water solubility) of a substance. The expectation is to be able to estimate the distribution coefficients of this substance in other systems with an aqueous and a lipophilic phase with the help of the octanol-water partition coefficient. Kow is greater than one when a substance is more soluble in fat-like solvents such as n-octanol, less than one when it is more soluble in water. Accordingly, Log Kow is positive for lipophilic and negative for hydrophilic substances.

Verbindungen mit log Kow › 0 mit der Bezeichnung X' umfassen erfindungsgemäß insbesondere (C2F6S2O4N)-, (BF4)-, B(C6H5)4 -, B(C6F5)4 -, B[C6H3(CF3)2]4, PF6 -, AsF6 -, SbF6-, [(C2F5)3PF3]-, C8H7-SO3 -, CnF2n+1-SO3 -, N(CN)2 -, CH2=C-CH3-COO(CH2)3(CF3S2O6N)-,-CH2=C-CH3-COO-(CH2)3(SO2NCN)-, CH2=C-CH3-COO-(CH2)3[SO2C(CN2)]-,CH2=CH-(C6H4)-(CF3S2O6N)-, CH2=CH-(C6H4)-(SO2NCN)-, CH2=CH-(C6H4)-[SO2C(CN2)]-, Cyanperfluoralkansulfonylamiden, Bis(cyan)perfluoralkansulfonylmethiden, Bis(perfluoralkansulfonyl)imiden, Bis(perfluoralkansulfonyl)methiden und Tris(perfluoralkansulfonyl)methiden C(SO2CF3)3 Compounds with log Kow> 0 with the designation X 'comprise according to the invention in particular (C 2 F 6 S 2 O 4 N) - , (BF 4 ) - , B (C 6 H 5 ) 4 - , B (C 6 F 5 ) 4 - , B [C 6 H 3 (CF 3 ) 2 ] 4 , PF 6 - , AsF 6 - , SbF 6 -, [(C 2 F 5 ) 3 PF 3 ] - , C 8 H 7 -SO 3 - , C n F 2n + 1 -SO 3 - , N (CN) 2 - , CH 2 = C-CH 3 -COO (CH 2 ) 3 (CF 3 S 2 O 6 N) - , -CH 2 = C- CH 3 -COO- (CH 2 ) 3 (SO 2 NCN) - , CH 2 = C-CH 3 -COO- (CH 2 ) 3 [ SO 2 C (CN 2 )] - , CH 2 = CH- (C 6 H 4 ) - (CF 3 S 2 O 6 N) - , CH 2 = CH- (C 6 H 4 ) - (SO 2 NCN) - , CH 2 = CH- (C 6 H 4 ) - [SO 2 C (CN 2 )] - , Cyanperfluoralkansulfonylamiden, bis (cyan) perfluoralkansulfonylmethiden, bis (perfluoroalkanesulfonyl) imides, bis (perfluoroalkanesulfonyl) methides and tris (perfluoroalkanesulfonyl) methides C (SO 2 CF 3 ) 3

Ferner werden Verbindungen der allgemeinen Formel (2)

Figure DE102016122626A1_0002
und Formel (3)
Figure DE102016122626A1_0003
beansprucht, die als Zwischen- und/oder Endprodukte bei der Synthese der polymerisierbaren Sulfobetaine erhalten werden.Furthermore, compounds of the general formula (2)
Figure DE102016122626A1_0002
 and formula (3)
Figure DE102016122626A1_0003
 which are obtained as intermediates and / or end products in the synthesis of the polymerizable sulfobetaines.

Des Weiteren wird ein Verfahren zur Herstellung der Verbindungen nach Formel (1) beansprucht, wonach eine Sulfobetain mit einem Thionylhalogenid, insbesondereThionylchlorid umgesetzt wird und nach der Umsetzung ein Phasenübergang des Reaktionsprodukts durch Zugabe von Strukturen X' erfolgt, wobei das Umsetzungsprodukt als Sulfobetainhalogenid erhalten wird.Furthermore, a process for the preparation of the compounds of formula (1) is claimed, after which a sulfobetaine is reacted with a thionyl halide, in particular thionyl chloride, and after the reaction a phase transition of the reaction product by addition of structures X ', the reaction product is obtained as Sulfobetainhalogenid.

Ein erhaltenes Sulfobetainhalogenid, insbesondere Sulfobetainchlorid kann mit einer Aminoverbindung, Thioverbindung, Hydroxyverbindung, Nitrilverbindung, Sulfonamidverbindung, insbesondere Malonsäuredinitril, Cyanamid, Anilin, -NH-Phenyl-SO2-NH2, -N-SO2-(CmF2m+1) mit m = 1 bis 10 umgesetzt werden, so dass insbesondere polymerisierbare sulfobetainsche Verbindungen der Formeln (4) bis (7)

Figure DE102016122626A1_0004
Figure DE102016122626A1_0005
Figure DE102016122626A1_0006
Figure DE102016122626A1_0007
erhalten werden können.A sulfobetaine halide obtained, in particular sulfobetaine chloride, can be reacted with an amino compound, thio compound, hydroxy compound, nitrile compound, sulfonamide compound, in particular malononitrile, cyanamide, aniline, -NH-phenyl-SO 2 -NH 2 , -N-SO 2 - (C m F 2m + 1 ) with m = 1 to 10, so that in particular polymerizable sulfobetaine compounds of the formulas (4) to (7)
Figure DE102016122626A1_0004
Figure DE102016122626A1_0005
Figure DE102016122626A1_0006
Figure DE102016122626A1_0007
 can be obtained.

Vorteilhafterweise kann das Sulfobetainhalogenid, insbesondere das Sulfobetainchlorid, mit einer Nitril-, Amino- oder Sulfonamidverbindung, insbesondere Malonsäuredinitril, Cyanamid, Perfluoralkansulfonamid, umgesetzt werden, wobei bei der Reaktion das Anion, welches zur Fällung verwendet wurde, insbesondere Lithium-bis(trifluormethansulfon)imid, zurückgewonnen wird, wenn wieder eine zwitterionische Verbindung entsteht.Advantageously, the sulfobetaine halide, in particular the sulfobetaine chloride, can be reacted with a nitrile, amino or sulfonamide compound, in particular malononitrile, cyanamide, perfluoroalkanesulfonamide, in which reaction the anion which was used for the precipitation, in particular lithium bis (trifluoromethanesulfone) imide, is recovered when a zwitterionic compound is formed again.

Weiterhin kann in einem vorteilhaften Verfahrensschritt eine Polymerisierung einer Verbindung, pro Molekül mindestens eine Ammoniumgruppe, mindestens eine Sulfonylgruppe, mindestens eine Cn-Alkyl-R4-Gruppe, eine Cn-Alkyl-OR4-Gruppe Cn-Alkyl-SR4-Gruppe oder Cn-Alkyl-NHR4-Gruppe enthält,
wobei R4 = Acryl, -Methacryl, -Vinyl, Cn-Alkyl, CO-CH3, -CO-CH2-CH3, -CO-(CH2)n-CH=CH-Phenyl, Phenyl, (CH2)n-Phenyl, -(CH2)n-Phenyl-CH-CH3, (CH2)n-N(CH3)2-(CH2)n-CH3, -CO-Phenyl-(CH2)n-CH3, -(CH2)n-C≡CH, -CO-NH-(CH-(CH3)2) und an die Cn-Alkyl tragende Ammoniumgruppe mindestens eine Gruppe Z gebunden ist,
wobei
Z = Cn-Alkyl-SO2-Y, -(CH2)n-SO2-Y, -(CH2)n-O-SO2-Y, -Phenyl-S-SO2-Y, -CH-(CH3)2-SO2-Y umfasst und Y= O, Cl, -OR4, -SR4, -NH-Phenyl, -NR4, -NH-Phenyl-SO2-NH2, -NH-R4, -N-SO2-(CmF2m+1), -N-CN, -C(CN)2 umfasst, und n = 0 bis 18 und m = 1 - 10 ist,
sowie deren Salze, Solvate und Solvate dieser Salze, insbesondere einer Verbindung der Formel 1, 2 und/oder 3 erfolgen, wobei die Polymerisation licht- oder wärmeinduziert erfolgt.Furthermore, in an advantageous process step, a polymerization of a compound, per molecule at least one ammonium group, at least one sulfonyl group, at least one C n alkyl R 4 group, a C n alkyl OR 4 group C n alkyl SR 4 Group or C n -alkyl-NHR 4 group,
wherein R 4 = acrylic, methacryl, vinyl, C n -alkyl, CO-CH 3 , -CO-CH 2 -CH 3 , -CO- (CH 2 ) n -CH = CH - phenyl, phenyl, (CH 2 ) n -phenyl, - (CH 2 ) n -phenyl-CH-CH 3 , (CH 2 ) n -N (CH 3 ) 2 - (CH 2 ) n -CH 3 , -CO-phenyl- (CH 2 ) n -CH 3 , - (CH 2 ) n -C≡CH, -CO-NH- (CH- (CH 3 ) 2 ) and to the C n -alkyl-bearing ammonium group at least one group Z is bound,
in which
Z = C n -alkyl-SO 2 -Y, - (CH 2 ) n -SO 2 -Y, - (CH 2 ) n -O-SO 2 -Y, -phenyl-S-SO 2 -Y, -CH - (CH 3 ) 2 -SO 2 -Y and Y = O, Cl, -OR 4 , -SR 4 , -NH-phenyl, -NR 4 , -NH-phenyl-SO 2 -NH 2 , -NH- R 4 , -N-SO 2 - comprises (C m F 2m + 1 ), -N-CN, -C (CN) 2 , and n = 0 to 18 and m = 1 to 10,
and their salts, solvates and solvates of these salts, in particular a compound of formula 1, 2 and / or 3, wherein the polymerization takes place light or heat induced.

Die beanspruchten Verbindungen der Formeln (1) bis (7) können zur Herstellung von anti-mikrobiellen Materialien, anti-statischen Materialien, anti-fouling Materialien, Druckfarben, oberflächenaktive Materialien für Beschichtungen und Lithografische Materialien zur Herstellung von Herbiziden, Fungiziden und Polymeren und zur Anwendung in der 2D-Gelelektrophorese und zur Anti-Haft-Beschichtung von Oberflächen verwendet werden.The claimed compounds of formulas (1) to (7) can be used for the preparation of anti-microbial materials, anti-static materials, anti-fouling materials, printing inks, surface-active materials for coatings and lithographic materials for the production of herbicides, fungicides and polymers and Use in 2D gel electrophoresis and for anti-adhesion coating of surfaces.

Die vorliegende Erfindung wird anhand der nachfolgenden Ausführungsbeispiele nochmals erläutert:The present invention will be explained again with reference to the following exemplary embodiments:

Synthesevorschrift für das NTf2-Sulfobetainchlorid:Synthesis instructions for the NTf 2 sulfobetaine chloride:

Figure DE102016122626A1_0008
Figure DE102016122626A1_0008

Das getrocknete [2-(Methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)-ammoniumhydroxid (16,76 g, 60 mmol) wird in 30 mL THF suspendiert und unter Stickstoffatmosphäre zunächst 1,7 mL DMF zugegeben. Danach wird die Reaktionsmischung auf 0-1 °C gekühlt und das Thionylchlorid (21,41 g, 180 mmol) unter Rühren langsam zugetropft. Nach erfolgter Zugabe wird zunächst eine Stunde bei 0-1 °C gerührt und anschließend noch 4h bei 40 °C, die Reaktionsmischung klart dabei auf.The dried [2- (methacryloyloxy) ethyl] dimethyl- (3-sulfopropyl) ammonium hydroxide (16.76 g, 60 mmol) is suspended in 30 mL THF and under a nitrogen atmosphere firstly 1.7 mL DMF are added. Thereafter, the reaction mixture is cooled to 0-1 ° C and the thionyl chloride (21.41 g, 180 mmol) slowly added dropwise with stirring. After the addition is first stirred for one hour at 0-1 ° C and then for 4 h at 40 ° C, the reaction mixture clears up.

Nach beendeter Reaktionszeit wird die Lösung vorsichtig auf 200 mL Eiswasser gegossen und in einen Scheidetrichter überführt. Anschließend wird eine Lösung aus Lithium-bis(trifluormethansulfon)imid (LiNTf2) (18,95 g, 66 mmol) gelöst in 50 mL Wasser langsam zugegeben. Das Produkt separiert sich dabei als ölige (untere) Phase und kann abgetrennt werden. Die wässrige Phase wird noch 2 mal mit 20 mL Dichlormathan extrahiert. Die organischen Phasen werden vereint und zusätzlich mit 60 mL Dichlormethan versetzt. Anschließend wird die Lösung zunächst 6 bis 8 mal mit jeweils 25 mL Wasser gewaschen und danach über Natrium- oder Magnesiumsulfat getrocknet.After completion of the reaction time, the solution is carefully poured onto 200 ml of ice water and transferred to a separating funnel. Subsequently, a solution of lithium bis (trifluoromethanesulfone) imide (LiNTf 2 ) (18.95 g, 66 mmol) dissolved in 50 mL of water is slowly added. The product separates as oily (lower) phase and can be separated. The aqueous phase is extracted twice more with 20 mL dichloromethane. The organic phases are combined and additionally combined with 60 mL dichloromethane. Subsequently, the solution is first washed 6 to 8 times with 25 ml of water and then dried over sodium or magnesium sulfate.

Das Lösemittel wird im darauf folgenden Schritt zunächst am Rotationsverdampfer bei Raumtemperatur und vermindertem Druck abgetrennt und das Produkt bei 5 mbar für 6 h weiter getrocknet.The solvent is first separated in a subsequent step on a rotary evaporator at room temperature and reduced pressure and the product is further dried at 5 mbar for 6 h.

allgemeine Synthesevorschrift für die ionischen Verbindungen: Am Beispiel der Umsetzung mit einer Aminoverbindung general synthesis instructions for the ionic compounds: The example of the reaction with an amino compound

Figure DE102016122626A1_0009
25 mmol einer Aminoverbindung werden in trockenem THF gelöst bzw. suspendiert und im Eiswasserbad auf 0 - 1 °C gekühlt. Danach wird die Mischung langsam und unter Rühren mit 120 mmol Triethylamin versetzt. Anschließend werden 25 mmol des NTf2-Säurechlorids gelöst in 20 mL THF langsam unter Rühren und weiterer Kühlung (unter 5 °C) zugetropft. Nach beendeter Zugabe wird der Ansatz zunächst 1 h bei unter 5 °C weitergerührt, danach zunächst auf RT erwärmt und im Anschluss noch 4 h bei 40 °C gerührt.
Figure DE102016122626A1_0009
 25 mmol of an amino compound are dissolved or suspended in dry THF and cooled to 0-1 ° C. in an ice-water bath. Thereafter, the mixture is added slowly and with stirring with 120 mmol of triethylamine. Subsequently, 25 mmol of the NTf 2 acid chloride dissolved in 20 ml of THF are slowly added dropwise with stirring and further cooling (below 5 ° C.). After completion of the addition, the mixture is first stirred for 1 h at below 5 ° C, then initially heated to RT and then stirred for 4 h at 40 ° C.

Aufarbeitung für Feststoffe: Nach beendeter Reaktionszeit wird der Ansatz auf RT abgekühlt, auf 200 mL Eiswasser gegossen. Der entstandene Niederschlag wird abfiltriert und mehrmals mit Wasser gewaschen. Anschließend wird das Produkt zunächst über Nacht bei RT und im Anschluss im Vakuumtrockenschrank bei 20 °C getrocknet.Work-up for solids: After the reaction time has ended, the batch is cooled to RT, poured onto 200 ml of ice-water. The resulting precipitate is filtered off and washed several times with water. Subsequently, the product is first dried overnight at RT and then in a vacuum oven at 20 ° C.

Aufarbeitung für Flüssigkeiten: Nach beendeter Reaktion wird der entstandene Niederschlag abfiltriert und das Filtrat vorsichtig am Rotationsverdampfer bei RT und vermindertem Druck eingeengt. Das erhaltene Öl wird danach in 50 mL Dichlormethan aufgenommen, 4 mal mit 20 mL Wasser gewaschen und anschließend über Natrium- oder Magnesiumsulfat getrocknet. Das Lösemittel wird danach am Rotationsverdampfer bei 30 °C und vermindertem abgetrennt und das Produkt bei RT und 5 mmbar für 4h getrocknet.Work-up for liquids: After the reaction has ended, the precipitate formed is filtered off and the filtrate is carefully concentrated by evaporation at RT and under reduced pressure on a rotary evaporator. The resulting oil is then taken up in 50 mL dichloromethane, washed 4 times with 20 mL water and then dried over sodium or magnesium sulfate. The solvent is then separated on a rotary evaporator at 30 ° C and reduced and the product dried at RT and 5 mmbar for 4 h.

Synthesevorschrift für inneren Salze:Synthesis instructions for internal salts:

Figure DE102016122626A1_0010
Figure DE102016122626A1_0010

Für den oberen Synthesepfad: For the upper synthesis path:

Reaktionsschritt 1: Trifluormethansulfonamid (3,72g, 25 mmol) wird in einen mit Stickstoff gespülten Kolben überführt und mit getrocknetem Triethylamin (5,57 g, 55 mmol) unter Rühren versetzt. Die Reaktionsmischung wird anschließend in 20 mL trockenem THF gelöst und auf 0 °C gekühlt. Dazu wird anschließend eine Lösung aus NTf2-Sulfobetainchlorid (14,47 g, 25 mmol) gelöst in 10 mL trockenem THF langsam unter Stickstoffatmosphäre und weitere Kühlung zugetropft. Die Reaktion läuft zunächst eine Stunde bei 0 °C und danach für eine weitere Stunde bei Raumtemperatur. Nach beendeter Reaktion wird der entstandene Niederschlag abfiltriert und das Filtrat vorsichtig am Rotationsverdampfer bei RT und vermindertem Druck eingeengt. Das erhaltene Öl wird danach in 50 mL Dichlormethan aufgenommen, 4 mal mit 20 mL Wasser gewaschen und anschließend über Natrium- oder Magnesiumsulfat getrocknet. Das Lösemittel wird danach am Rotationsverdampfer bei 30 ° C und vermindertem abgetrennnt und das Produkt bei RT und 5 mmbar für 4h getrocknet. Reaction Step 1: Trifluoromethanesulfonamide (3.72 g, 25 mmol) is transferred to a flask purged with nitrogen and treated with dried triethylamine (5.57 g, 55 mmol) with stirring. The reaction mixture is then dissolved in 20 mL of dry THF and cooled to 0 ° C. For this purpose, a solution of NTf 2 -Sulfobetainchlorid (14.47 g, 25 mmol) dissolved in 10 mL of dry THF is then added dropwise slowly under a nitrogen atmosphere and further cooling. The reaction first proceeds for one hour at 0 ° C and then for a further hour at room temperature. After completion of the reaction, the precipitate formed is filtered off and the filtrate is carefully concentrated by evaporation on a rotary evaporator at RT and under reduced pressure. The resulting oil is then taken up in 50 mL dichloromethane, washed 4 times with 20 mL water and then dried over sodium or magnesium sulfate. The solvent is then separated on a rotary evaporator at 30 ° C and reduced and the product dried at RT and 5 mmbar for 4 h.

Reaktionsschritt 2: Das Zwischenprodukt aus dem ersten Reaktionsschritt wird in 25 mL trockenem THF unter N2-Atmosphäre gelöst und auf 0 °C gekühlt. Anschließend wird eine Suspension aus LiH (0,28g, 35 mmol) und 10 mL trockenem THF langsam zugetropft. Das Eisbad wird danach entfernt und die Raktionsmischung langsam auf RT erwärmt. Nach 2 Stunden Rühren bei Raumtemperatur wird das nicht umgesetzte LiH abfiltiert und das Filtrat bei vermindertem Druck eingeengt. Der ölige Rückstand wird danach mehrmals mit n-Hexan extrahiert um das LiNTf2 zurückzugewinnen. Das Produkt wird zunächst bei RT und 20 mmbar vorgetrocknet und anschließend bei 5 mmbar im Vakuumtrockenschrank ebenfalls bei RT getrocknet. Man erhält einen leicht beigen Feststoff.Reaction Step 2: The intermediate from the first reaction step is dissolved in 25 mL dry THF under N 2 atmosphere and cooled to 0 ° C. Subsequently, a suspension of LiH (0.28 g, 35 mmol) and 10 mL dry THF is slowly added dropwise. The ice bath is then removed and the reaction mixture slowly warmed to rt. After stirring for 2 hours at room temperature, the unreacted LiH is filtered off and the filtrate is concentrated under reduced pressure. The oily residue is then extracted several times with n-hexane to recover the LiNTf 2 . The product is first predried at RT and 20 mmbar and then dried at 5 mmbar in a vacuum oven also at RT. This gives a slightly beige solid.

Synthese weitere innerer Salze:Synthesis of other internal salts:

Die Synthese der weiteren zwei oben aufgeführten Verbindungen erfolgte in Analogie. Es wurde dafür anstatt des Triflurmethansulfonamids entweder Malonsäuredinitril (mittlere Reaktion) oder Cyanamid (untere Reaktion) verwendet.The synthesis of the other two compounds listed above was carried out in analogy. Instead of the trifluoromethanesulfonamide either malononitrile (middle reaction) or cyanamide (lower reaction) was used instead.

ZITATE ENTHALTEN IN DER BESCHREIBUNG QUOTES INCLUDE IN THE DESCRIPTION

Diese Liste der vom Anmelder aufgeführten Dokumente wurde automatisiert erzeugt und ist ausschließlich zur besseren Information des Lesers aufgenommen. Die Liste ist nicht Bestandteil der deutschen Patent- bzw. Gebrauchsmusteranmeldung. Das DPMA übernimmt keinerlei Haftung für etwaige Fehler oder Auslassungen.This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Zitierte PatentliteraturCited patent literature

  • US 2433997 A [0004]US 2433997 A [0004]

Claims (15)

Ionische Verbindungen, die pro Molekül mindestens eine Ammoniumgruppe, mindestens eine Sulfonylgruppe, mindestens eine Cn-Alkyl-Gruppe, eine Cn-Alkyl-R4-Gruppe, eine Cn-Alkyl-OR4-Gruppe, Cn-Alkyl-SR4-Gruppe oder Cn-Alkyl-NHR4-Gruppe enthält, wobei R4 = Cn-Alkyl, CO-CH3, -CO-CH2-CH3, -CO-NH2, Phenyl, (CH2)n-Phenyl, -(CH2)n-Phenyl-CH-CH3, (CH2)n-N(CH3)2-(CH2)n-CH3, -CO-Phenyl-(CH2)n-CH3, -CO-NH-(CH-(CH3)2) und an die C1-Cn-Alkyl tragende Ammoniumgruppe mindestens eine Gruppe Z gebunden ist, wobei Z = Cn-Alkyl-SO2-Y, -(CH2)n-SO2-Y, -(CH2)n-O-SO2-Y, -Phenyl-S-SO2-Y, -CH-(CH3)2-SO2-Y umfasst und Y = O, Cl, -OR4, -SR4, -NH-Phenyl, -NR4, -NH-Phenyl-SO2-NH2, -NH-R4, -N-SO2-(CmF2m+1), -N-CN, -C(CN)2, umfasst, und n = 0 bis 18 und m = 1 bis 10 ist, sowie deren Salze, Solvate und Solvate dieser Salze.Ionic compounds containing, per molecule, at least one ammonium group, at least one sulfonyl group, at least one C n -alkyl group, one C n -alkyl-R 4 -group, one C n -alkyl-OR 4 -group, C n -alkyl- SR 4 group or C 1 -C 4 alkylNHR 4 group, wherein R 4 = C n -alkyl, CO-CH 3 , -CO-CH 2 -CH 3 , -CO-NH 2 , phenyl, (CH 2 ) n- phenyl, - (CH 2 ) n -phenyl-CH-CH 3 , (CH 2 ) n -N (CH 3 ) 2 - (CH 2 ) n -CH 3 , -CO-phenyl- (CH 2 ) n -CH 3 , -CO-NH- (CH- (CH 3 ) 2 ) and to the C 1 -C n -alkyl-bearing ammonium group is bound at least one group Z, wherein Z = C n -alkyl-SO 2 -Y, - (CH 2 ) n -SO 2 -Y, - (CH 2 ) n -O-SO 2 -Y, -phenyl-S-SO 2 -Y, -CH- (CH 3 ) 2 -SO 2 -Y and Y = O, Cl, -OR 4 , -SR 4 , -NH-phenyl, -NR 4, -NH-phenyl-SO 2 -NH 2 , -NH-R 4 , -N-SO 2 - (C m F 2m +1 ), -N-CN, -C (CN) 2, and n = 0 to 18 and m = 1 to 10, and their salts, solvates and solvates of these salts. Ionische Verbindungen nach Anspruch 1, wobei pro Molekül die mindestens eine Ammoniumgruppe, die mindestens eine Sulfonylgruppe, die mindestens eine Cn-Alkyl-Gruppe eine Cn-Alkyl-R4-Gruppe, eine Cn-Alkyl- OR4-Gruppe, die Cn-Alkyl-SR4-Gruppe oder die Cn-Alkyl-NHR4-Gruppe wobei R4 zusätzlich eine Acryl, -Methacryl-, Vinylgruppe oder-(CH2)n-C=CH umfasst und n = 0 bis 18 ist, sowie deren Salze, Solvate und Solvate dieser Salze.Ionic compounds according to Claim 1 in which, per molecule, the at least one ammonium group, the at least one sulfonyl group, the at least one C n -alkyl group, a C n -alkyl-R 4 group, a C n -alkyl-OR 4 group, the C n -alkyl -SR 4 group or the C n -alkyl-NHR 4 group wherein R 4 additionally comprises an acrylic, methacrylic, vinyl group or- (CH 2 ) n -C = CH and n = 0 to 18, and their Salts, solvates and solvates of these salts. Ionische Verbindungen nach Anspruch 1 oder 2 der Formel (1)
Figure DE102016122626A1_0011
wobei Z = Cn-Alkyl-SO2-Y, -(CH2)n-SO2-Y, -(CH2)n-O-SO2-Y, -Phenyl-S-SO2-Y, -CH-(CH3)2-SO2-Y, R1 = H, Cn-Alkyl, Cn-Alkyl-R4, Cn-Alkyl-OR4, Cn-Alkyl-SR4 oder Cn-Alkyl-NHR4 R2 = H, Cn-Alkyl, Cn-Alkyl-R4, Cn-Alkyl-OR4, Cn-Alkyl-SR4 oder Cn-Alkyl-NHR4 R3 = H, Cn-Alkyl, Cn-Alkyl-R4, Cn-Alkyl-OR4, Cn-Alkyl-SR4 oder Cn-Alkyl-NHR4 R1 = R2 = R3 = mehrfach, allein oder unabhängig voneinander sein kann, sowie (C1nH2n-O)n, (C1nH2n)n, 1,4-Diazobicylco [2.2.] octane, 1-Azoniabicyclo [2.2.2] octane, 4-Aza-1-azoniabicyclo [2.2.2] octane umfasst, A = N, Imidazole, Pyridine, Pyrimidine, Triazole, Tetrazole, Benzimidazole, Thiazole, Thiadiazole, Benzothiazole, Morpholine R4 = Acryl, -Methacryl, -Vinyl, Cn-Alkyl, CO-CH3, -CO-CH2-CH3, -CO-(CH2)n-CH=CH-Phenyl, Phenyl, (CH2)n-Phenyl, -(CH2)n-Phenyl-CH-CH3, (CH2)n-N(CH3)2-(CH2)n-CH3, -CO-Phenyl-(CH2)n-CH3, -(CH2)n-C≡CH, -CO-NH-(CH-(CH3), Y = O, Cl, -OR4, -SR4, -NH-Phenyl, -NR4, -NH-Phenyl-SO2-NH2, -NH-R4, -N-SO2-(CmF2m+1), -N-CN, -C(CN)2 X' = Verbindung, die zumindest eine Hydrophobizität mit einem Verteilungskoeffizienten log Kow › 0 aufweist und n = 0 - 18 umfasst und m = 1 - 10.Ionic compounds according to Claim 1 or 2 of the formula (1)
Figure DE102016122626A1_0011
 where Z = C n -alkyl-SO 2 -Y, - (CH 2 ) n -SO 2 -Y, - (CH 2 ) n -O-SO 2 -Y, -phenyl-S-SO 2 -Y, - CH (CH 3 ) 2 -SO 2 -Y, R 1 = H, C n -alkyl, C n -alkyl-R 4 , C n -alkyl-OR 4 , C n -alkyl-SR 4 or C n - Alkyl-NHR 4 R 2 = H, C n -alkyl, C n -alkyl-R 4 , C n -alkyl-OR 4 , C n -alkyl-SR 4 or C n -alkyl-NHR 4 R 3 = H, C n alkyl, C n alkyl R 4 , C n alkyl OR 4 , C n alkyl SR 4 or C n alkyl NHR 4 R 1 = R 2 = R 3 = multiple, alone or independently (C 1n H 2n- O) n , (C 1n H 2n ) n , 1,4-diazobicylco [2.2.] octane, 1-azoniabicyclo [2.2.2] octane, 4-aza-1 azoniabicyclo [2.2.2] octane, A = N, imidazoles, pyridines, pyrimidines, triazoles, tetrazoles, benzimidazoles, thiazoles, thiadiazoles, benzothiazoles, morpholines R 4 = acrylic, methacryl, vinyl, C n -alkyl, CO- CH 3 , -CO-CH 2 -CH 3 , -CO- (CH 2 ) n -CH = CH - phenyl, phenyl, (CH 2 ) n -phenyl, - (CH 2 ) n -phenyl-CH-CH 3 , (CH 2 ) n -N (CH 3 ) 2 - (CH 2 ) n -CH 3 , -CO-phenyl- (CH 2 ) n -CH 3 , - (CH 2 ) n -C≡CH, -CO-NH- (CH- (CH 3 ), Y = O, Cl, -OR 4 , -SR 4 , -NH-phenyl, -NR 4 , -NH-phenyl-SO 2 -NH 2 , -NH- R 4 , -N-SO 2 - (C m F 2m + 1 ), -N-CN, -C (CN) 2 X '= compound which has at least one hydrophobicity with a distribution coefficient log Kow> 0 and n = 0 - 18 includes and m = 1 - 10. Ionische Verbindungen nach Anspruch 1 bis 3, dadurch gekennzeichnet, dass Verbindungen der Formel (1) insbesondere der Formel (2)
Figure DE102016122626A1_0012
umfasst sind.Ionic compounds according to Claim 1 to 3 Characterized in that compounds of the formula (1) in particular of formula (2)
Figure DE102016122626A1_0012
 are included. Ionische Verbindungen nach Anspruch 1 bis 4, dadurch gekennzeichnet, dass Verbindungen der Formel (1), insbesondere der Formel (3)
Figure DE102016122626A1_0013
umfasst sind.Ionic compounds according to Claim 1 to 4 , characterized in that compounds of the formula (1), in particular of the formula (3)
Figure DE102016122626A1_0013
 are included. Ionische Verbindungen nach Anspruch 1 bis 5, dadurch gekennzeichnet, dass X- = (C2F6S2O4N)-, (BF4)-, B(C6H5)4 -, B(C6F5)4 -, B[C6H3(CF3)2]4, PF6 -, AsF6 -, SbF6 -, [(C2F5)3PF3]-, C8H7-SO3 -, CnF2n+1-SO3 -, N(CN)2 -, CH2=C-CH3-COO-(CH2)3(CF3S2O6N)-, CH2=C-CH3-COO-(CH2)3(SO2NCN)-, CH2=C-CH3-COO-(CH2)3[SO2C(CN2)]-, CH2=CH-(C6H4)-(CF3S2O6N)-, CH2=CH-(C6H4)-(SO2NCN)-, CH2=CH-(C6H4)-[SO2C(CN2)]-, Cyanperfluoralkansulfonylamide, Bis(cyan)perfluoralkansulfonylmethide, Bis(perfluoralkansulfonyl)imide, Bis(perfluoralkansulfonyl)methide und Tris(perfluoralkansulfonyl)methide umfasst.Ionic compounds according to Claim 1 to 5 , characterized in that X - = (C 2 F 6 S 2 O 4 N) - , (BF 4 ) - , B (C 6 H 5 ) 4 - , B (C 6 F 5 ) 4 - , B [C 6 H 3 (CF 3 ) 2 ] 4 , PF 6 - , AsF 6 - , SbF 6 - , [(C 2 F 5 ) 3 PF 3 ] - , C 8 H 7 -SO 3 - , C n F 2n + 1 -SO 3 - , N (CN) 2 - , CH 2 = C-CH 3 -COO- (CH 2 ) 3 (CF 3 S 2 O 6 N) - , CH 2 = C-CH 3 -COO- CH 2 ) 3 (SO 2 NCN) - , CH 2 = C-CH 3 -COO- (CH 2 ) 3 [SO 2 C (CN 2 )] - , CH 2 = CH- (C 6 H 4 ) - ( CF 3 S 2 O 6 N) - , CH 2 = CH- (C 6 H 4 ) - (SO 2 NCN) - , CH 2 = CH- (C 6 H 4 ) - [SO 2 C (CN 2 )] -, Cyanperfluoralkansulfonylamide, bis (cyan) perfluoralkansulfonylmethide, bis (perfluoroalkanesulfonyl) imides, bis (perfluoroalkanesulfonyl) methides, and tris (perfluoroalkanesulfonyl) methides comprises. Verfahren zur Herstellung ionischer Verbindungen die pro Molekül mindestens eine Ammoniumgruppe, mindestens eine Sulfonylgruppe, mindestens eine Cn-Alkyl-Gruppe, Cn-Alkyl-R4-Gruppe, Cn-Alkyl-OR4-Gruppe, Cn-Alkyl-SR4-Gruppe oder Cn-Alkyl-NHR4-Gruppe enthält, wobei R4= Acryl, -Methacryl, -Vinyl, Cn-Alkyl, CO-CH3, -CO-CH2-CH3, -CO-(CH2)n-CH=CH-Phenyl, Phenyl, (CH2)n-Phenyl, -(CH2)n-Phenyl-CH-CH3, (CH2)n-N(CH3)2-(CH2)n-CH3, -CO-Phenyl-(CH2)n-CH3, -(CH2)n-C≡CH, -CO-NH-(CH-(CH3)2) und an die Cn-Alkyl tragende Ammoniumgruppe mindestens eine Gruppe Z gebunden ist, wobei Z = Cn-Alkyl-SO2-Y, -(CH2)n-SO2-Y, -(CH2)n-O-SO2-Y, -Phenyl-S-SO2-Y, -CH-(CH3)2-SO2-Y umfasst und Y = -O, -Cl, -OR4, -SR4, -NH-Phenyl, -NR4, -NH-Phenyl-SO2-NH2, -NH-R4, -N-SO2-(CmF2m+1), -N-CN, -C(CN)2 umfasst, und n = 0 bis 18 und m = 1 - 10 ist, sowie deren Salze, Solvate und Solvate dieser Salze, dadurch gekennzeichnet, dass ein Sulfobetain mit einem Thionylhalogenid umgesetzt wird und nach der Umsetzung ein Phasenübergang des Reaktionsprodukts durch Zugabe von Strukturen X' erfolgt, wobei das Umsetzungsprodukt als Sulfobetainhalogenid erhalten wird.Process for the preparation of ionic compounds which contain per molecule at least one ammonium group, at least one sulfonyl group, at least one C n -alkyl group, C n -alkyl-R 4 -group, C n -alkyl-OR 4 -group, C n -alkyl- SR 4 group or C n -alkyl-NHR 4 group, where R 4 = acryl, methacryl, vinyl, C n -alkyl, CO-CH 3 , -CO-CH 2 -CH 3 , -CO- (CH 2 ) n -CH = CH - phenyl, phenyl, (CH 2 ) n -phenyl, - (CH 2 ) n -phenyl-CH-CH 3 , (CH 2 ) n -N (CH 3 ) 2 - ( CH 2 ) n -CH 3 , -CO-phenyl- (CH 2 ) n -CH 3 , - (CH 2 ) n -C≡CH, -CO-NH- (CH- (CH 3 ) 2 ) and to the C n -alkyl-bearing ammonium group is bonded to at least one group Z, where Z = C n -alkyl-SO 2 -Y, - (CH 2 ) n -SO 2 -Y, - (CH 2 ) n -O-SO 2 - Y, -phenyl-S-SO 2 -Y, -CH- (CH 3 ) 2 -SO 2 -Y and Y = -O, -Cl, -OR 4 , -SR 4 , -NH-phenyl, -NR 4 , -NH-phenyl-SO 2 -NH 2 , -NH-R 4 , -N-SO 2 - (CmF 2m + 1 ), -N-CN, -C (CN) 2 , and n = 0 to 18 and m = 1-10, as well as their salts, solvates and solvates of these salts, characterized in that a sulfobetaine is reacted with a thionyl halide and after the reaction, a phase transition of the reaction product by addition of structures X ', wherein the reaction product is obtained as Sulfobetainhalogenid. Verfahren nach Anspruch 7, dadurch gekennzeichnet, dass die ionische Verbindung pro Molekül mindestens eine Ammoniumgruppe, mindestens eine Sulfonylgruppe, mindestens eine Cn-Alkyl-Gruppe, Cn-Alkyl-R4-Gruppe, Cn-Alkyl-OR4-Gruppe, Cn-Alkyl- SR4-Gruppe oder Cn-Alkyl-NHR4-Gruppe umfasst, wobei R4 zusätzlich eine Acryl, -Methacryl-, Vinylgruppe oder-(CH2)n-C≡CH beinhaltet, wobei n = 0 bis 18 ist.Method according to Claim 7 Characterized in that the ionic compound per molecule at least one ammonium group, at least one sulfonyl group, at least one C n alkyl group, C n -alkyl-R 4 group, C n -alkyl-OR 4 group, C n - Alkyl-SR 4 group or C n -alkyl-NHR 4 group, wherein R 4 additionally includes an acrylic, methacrylic, vinyl group or- (CH 2 ) n -C≡CH, where n = 0 to 18 , Verfahren nach Anspruch 7 oder 8, dadurch gekennzeichnet, dass ionische Verbindungen der Formel (1)
Figure DE102016122626A1_0014
umfasst sind, wobei Z = Cn-Alkyl-SO2-Y, -(CH2)n-SO2-Y, -(CH2)n-O-SO2-Y, -Phenyl-S-SO2-Y, -CH-(CH3)2-SO2-Y, R1 = H, Cn-Alkyl, Cn-Alkyl-R4, Cn-Alkyl-OR4, Cn-Alkyl-SR4 oder Cn-Alkyl-NHR4 R2 = H, Cn-Alkyl, Cn-Alkyl-R4, Cn-Alkyl-OR4, Cn-Alkyl-SR4 oder Cn-Alkyl-NHR4 R3 = H, Cn-Alkyl, Cn-Alkyl-R4, Cn-Alkyl-OR4, Cn-Alkyl-SR4 oder Cn-Alkyl-NHR4 R1 = R2 = R3 = mehrfach, allein oder unabhängig voneinander sein kann, sowie (C1nH2n-O)n, (C1nH2n)n, 1,4-Diazobicylco [2.2.] octane, 1-Azoniabicyclo [2.2.2] octane, 4-Aza-1-azoniabicyclo [2.2.2] octane umfasst, A = N, Imidazole, Pyridine, Pyrimidine, Triazole, Tetrazole, Benzimidazole, Thiazole, Thiadiazole, Benzothiazole, Morpholine R4 = Acryl, -Methacryl, -Vinyl, Cn-Alkyl, CO-CH3, -CO-CH2-CH3, -CO-(CH2)n-CH=CH-Phenyl, Phenyl, (CH2)n-Phenyl, -(CH2)n-Phenyl-CH-CH3, (CH2)n-N(CH3)2-(CH2)n-CH3, -CO-Phenyl-(CH2)n-CH3, -(CH2)n-C≡CH, -CO-NH-(CH-(CH3), Y = O, Cl, -OR4, -SR4, -NH-Phenyl, -NR4, -NH-Phenyl-SO2-NH2, -NH-R4, -N-SO2-(CmF2m+1), -N-CN, -C(CN)2 X' = Verbindung, die zumindest eine Hydrophobizität mit einem Verteilungskoeffizienten log Kow › 0 aufweist und n = 0 - 18 umfasst und m = 1 - 10.Method according to Claim 7 or 8th , characterized in that ionic compounds of the formula (1)
Figure DE102016122626A1_0014
 wherein Z is C n -alkyl-SO 2 -Y, - (CH 2 ) n -SO 2 -Y, - (CH 2 ) n -O-SO 2 -Y, -phenyl-S-SO 2 - Y, -CH- (CH 3 ) 2 -SO 2 -Y, R 1 = H, C n -alkyl, C n -alkyl-R 4 , C n -alkyl-OR 4 , C n -alkyl-SR 4 or C n -alkyl-NHR 4 R 2 = H, C n -alkyl, C n -alkyl-R 4 , C n -alkyl-OR 4 , C n -alkyl-SR 4 or C n -alkyl-NHR 4 R 3 = H, C n -alkyl, C n -alkyl-R 4 , C n -alkyl-OR 4 , C n -alkyl-SR 4 or C n -alkyl-NHR 4 R 1 = R 2 = R 3 = multiple, or (C 1n H 2n- O) n , (C 1n H 2n ) n , 1,4-diazobicylco [2.2.] octane, 1-azoniabicyclo [2.2.2] octane, 4-aza 1-azoniabicyclo [2.2.2] octanes, A = N, imidazoles, pyridines, pyrimidines, triazoles, tetrazoles, benzimidazoles, thiazoles, thiadiazoles, benzothiazoles, morpholines R 4 = acrylic, methacryl, vinyl, C n -alkyl , CO-CH 3 , -CO-CH 2 -CH 3 , -CO- (CH 2 ) n -CH = CH - phenyl, phenyl, (CH 2 ) n -phenyl, - (CH 2 ) n -phenyl-CH -CH 3 , (CH 2 ) n -N (CH 3 ) 2 - (CH 2 ) n -CH 3 , -CO-phenyl- (CH 2 ) n -CH 3 , - (CH 2 ) n -C≡CH, -CO-NH- (CH- (CH 3 ), Y = O, Cl, -OR 4 , -SR 4 , -NH-phenyl, -NR 4 , -NH-phenyl-SO 2 -NH 2 , -NH-R 4 , -N-SO 2 - (C m F 2m + 1 ), -N-CN, -C (CN) 2 X '= compound having at least one hydrophobicity with a distribution coefficient log Kow > 0 and n = 0-18 and m = 1-10. Verfahren nach Anspruch 7 bis 9, dadurch gekennzeichnet, dass das Sulfobetainhalogenid, insbesondere Sulfobetainchlorid mit einer Sulfonamid-, Amino-, Thio-, Hydroxy- oder Nitrilverbindung, insbesondere Malonsäuredinitril, Cyanamid, -N-SO2-(CmF2m+1), Anilin, -NH-Phenyl-SO2-NH2 zu einem Sulfonamid, Sulfonimid, Sulfonmethid, Thiosulfonsäureester bzw. Sulfonsäureester umgesetzt wird, wobei m = 1 bis 10 ist.Method according to Claim 7 to 9 , characterized in that the sulfobetaine halide, in particular sulfobetaine chloride with a sulfonamide, amino, thio, hydroxy or nitrile compound, in particular malononitrile, cyanamide, -N-SO 2 - (CmF 2m + 1 ), aniline, -NH-phenyl -SO 2 -NH 2 is converted to a sulfonamide, sulfonimide, sulfone methide, thiosulfonic acid ester or sulfonic acid ester, where m = 1 to 10. Verfahren nach Anspruch 7 bis 10, dadurch gekennzeichnet, dass bei der Umsetzung des Sulfobetainhalogenids, insbesondere Sulfobetainchlorids mit der Sulfonamid-, Amino- oder der Nitrilverbindung zurückgewonnen wird, wenn wieder eine zwitterionische Verbindung entsteht.Method according to Claim 7 to 10 , characterized in that in the implementation of the Sulfobetainhalogenids, in particular Sulfobetainchlorids with the sulfonamide, amino or nitrile compound is recovered when a zwitterionic compound is formed again. Verfahren nach Anspruch 7 bis 11, dadurch gekennzeichnet, dass eine Polymerisierung einer Verbindung erfolgt, die pro Molekül mindestens eine Ammoniumgruppe, mindestens eine Sulfonylgruppe, mindestens eine Cn-Alkyl-Gruppe, Cn-Alkyl-R4-Gruppe, Cn-Alkyl-OR4-Gruppe, Cn-Alkyl-SR4-Gruppe oder Cn-Alkyl-NHR4-Gruppe enthält, wobei R4 = Acryl, -Methacryl, -Vinyl, Cn-Alkyl, CO-CH3, -CO-CH2-CH3, -CO-(CH2)n-CH=CH-Phenyl, Phenyl, (CH2)n-Phenyl, -(CH2)n-Phenyl-CH-CH3, (CH2)n-N(CH3)2-(CH2)n-CH3, -CO-Phenyl-(CH2)n-CH3, -(CH2)n-C≡CH, -CO-NH-(CH-(CH3)2) und an die Cn-Alkyl tragende Ammoniumgruppe mindestens eine Gruppe Z gebunden ist, wobei Z = Cn-Alkyl-SO2-Y, -(CH2)n-SO2-Y, -(CH2)n-O-SO2-Y, -Phenyl-S-SO2-Y, -CH-(CH3)2-SO2-Y umfasst und Y = -O, -Cl, -OR4, -SR4, -NH-Phenyl, -NR4, -NH-Phenyl-SO2-NH2, -NH-R4, -N-SO2-(CmF2m+1), -N-CN, -C(CN)2 umfasst, und n = 0 bis 18 und m = 1 - 10 ist, sowie deren Salze, Solvate und Solvate dieser Salze, insbesondere einer Verbindung der Formel 1, 2 und/oder 3, wobei die Polymerisation licht- oder wärmeinduziert ist.Method according to Claim 7 to 11 , characterized in that a polymerization of a compound is carried out, the per molecule at least one ammonium group, at least one sulfonyl group, at least one C n alkyl group, C n alkyl R 4 group, C n alkyl OR 4 group Contains C n -alkyl-SR 4 -group or C n -alkyl-NHR 4 -group, wherein R 4 = acrylic, methacryl, vinyl, C n alkyl, CO-CH 3 , -CO-CH 2 -CH 3 , -CO- (CH 2 ) n -CH = CH-phenyl, phenyl, (CH 2) n -phenyl, - (CH 2) n -phenyl-CH-CH 3, (CH 2) n -N (CH 3) 2 - (CH 2) n -CH 3, -CO-phenyl- (CH 2) n -CH 3 , - (CH 2 ) n -C≡CH, -CO-NH- (CH- (CH 3 ) 2 ) and to the C n -Alkyl carrying ammonium group is bound at least one group Z, wherein Z = C n -Alkyl-SO 2 -Y, - (CH 2 ) n -SO 2 -Y, - (CH 2 ) n -O-SO 2 -Y, -phenyl-S-SO 2 -Y, -CH- (CH 3 ) 2 -SO 2 -Y and Y = -O, -Cl, -OR 4 , -SR 4 , -NH-phenyl, -NR 4 , -NH-phenyl-SO 2 -NH 2 , -NH-R 4 , -N-SO 2 - (CmF 2m + 1 ), -N-CN, -C (CN) 2 , and n = 0 to 18 and m = 1-10, and their salts, solvates and solvates thereof Salts, in particular a compound of formula 1, 2 and / or 3, wherein the polymerization is light- or heat-induced. Verwendung von ionischen Verbindungen nach Anspruch 1 bis 6 zur Herstellung von anti-mikrobiellen Materialien, anti-statischen Materialien, anti-fouling Materialien, Druckfarben, oberflächenaktive Materialien für Beschichtungen und Lithografische Materialien.Use of ionic compounds according to Claim 1 to 6 for the production of anti-microbial materials, anti-static materials, anti-fouling materials, printing inks, surface-active materials for coatings and lithographic materials. Verwendung von ionischen Verbindungen nach Anspruch 11 zur Anwendung in der 2D-Gelelektrophorese und zur Anti-Haft-Beschichtung von Oberflächen.Use of ionic compounds according to Claim 11 for use in 2D gel electrophoresis and for anti-adhesion coating of surfaces. Verwendung von ionischen Verbindungen nach Anspruch 11 zur Herstellung von Herbiziden, Fungiziden und Polymeren.Use of ionic compounds according to Claim 11 for the production of herbicides, fungicides and polymers.
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US2433997A (en) 1944-04-24 1948-01-06 Du Pont Quaternary ammonium sulfone halides
WO2017135186A1 (en) * 2016-02-01 2017-08-10 富士フイルム株式会社 Root canal treatment material and kit for root canal treatment

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* Cited by examiner, † Cited by third party
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US2433997A (en) 1944-04-24 1948-01-06 Du Pont Quaternary ammonium sulfone halides
WO2017135186A1 (en) * 2016-02-01 2017-08-10 富士フイルム株式会社 Root canal treatment material and kit for root canal treatment

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